This thesis presents the analysis, design and characterization of an integrated high-frequency phase-locked loop (PLL) frequency multiplier. The frequency multiplier is novel in its use of a low multiplication factor of 4 and a fully differential topology for rejection of common mode interference signals. The PLL is composed of a voltage controlled oscillator (VCO), injection-locked frequency divider (ILFD) for the first divide-by-two stage, a static master-slave flip-flop (MSFF) divider for the second divide-by-two stage and a Gilbert cell mixer phase detector (PD). The circuit has been fabricated using a standard CMOS 0.18-um process based on its relatively low cost and ready availability. The PLL frequency multiplier generates an output signal at 26 GHz and is the highest operational frequency PLL in the technology node reported to date. Time domain phase plane analysis is used for prediction of PLL locking range based on initial conditions of phase and frequency offsets. Tracking range of the PLL is limited by the inherent narrow locking range of the ILFD, and is confirmed via experimental results. The performance benefits of the fully differential PLL are experimentally confirmed by the injection of differential- and common-mode interfering signals at the VCO control lines. A comparison of the common- and differential-mode modulation indices reveals that a common mode rejection ratio (CMRR) of greater than 20 dB is possible for carrier offset frequencies of less than 1 MHz. Closed-loop frequency domain transfer functions are used for prediction of the PLL phase noise response, with the PLL being dominated by the reference and VCO phase noise contributions. Regions of dominant phase noise contributions are presented and correlated to the overall PLL phase noise performance. Experimental verifications display good agreement and confirm the usefulness of the techniques for PLL performance prediction. The PLL clock multiplier has an operational output frequency of 26.204 to 26.796 GHz and a maximum output frequency step of 16 MHz. Measured phase noise at 1 MHz offset from the carrier is -103.9 dBc/Hz. The PLL clock multiplier core circuit (VCO/ILFD/MSFF Divider/PD) consumes 186 mW of combined power from 2.8 and 4.3 V DC rails. / Thesis (Ph.D, Electrical & Computer Engineering) -- Queen's University, 2009-04-24 11:31:35.384

Ferroelectric field effect transistor (FeFET) memories based on a new type of ferroelectric material (silicon doped hafnium oxide) were studied within the scope of the present work. Utilisation of silicon doped hafnium oxide (Si:HfO2) thin films instead of conventional perovskite ferroelectrics as a functional layer in FeFETs provides compatibility to the CMOS process as well as improved device scalability. The influence of different process parameters on the properties of Si:HfO2 thin films was analysed in order to gain better insight into the occurrence of ferroelectricity in this system. A subsequent examination of the potential of this material as well as its possible limitations with the respect to the application in non-volatile memories followed. The Si:HfO2-based ferroelectric transistors that were fully integrated into the state-of-the-art high-k metal gate CMOS technology were studied in this work for the first time. The memory performance of these devices scaled down to 28 nm gate length was investigated. Special attention was paid to the charge trapping phenomenon shown to significantly affect the device behaviour.

L'objectif principal de cette thèse est de proposer et d'évaluer une nouvelle architecture de Transistor Bipolaire à Héterojonction (TBH) Si/SiGe s’affranchissant des limitations de l'architecture conventionnelle DPSA-SEG (Double-Polysilicium Self-Aligned, Selective Epitaxial Growth) utilisée dans la technologie 55 nm Si/SiGe BiCMOS (BiCMOS055) de STMicroelectronics. Cette nouvelle architecture est conçue pour être compatible avec la technologie 28-nm FD-SOI (Fully Depleted Si-licon On Insulator), avec pour objectif d'atteindre la performance de 400 GHz de fT et 600 GHz de fMAX dans ce noeud. Pour atteindre cet objectif ambitieux, plusieurs études complémentaires ont été menées: 1/ l'exploration et la comparaison de différentes architectures de TBH SiGe, 2/ l'étalonnage TCAD en BiCMOS055, 3/ l'étude du budget thermique induit par la fabrication des technologies BiCMOS, et finalement 4/ l'étude d'une architecture innovante et son optimisation. Les procédés de fabrication ainsi que les modèles physiques (comprenant le rétrécissement de la bande interdite, la vitesse de saturation, la mobilité à fort champ, la recombinaison SRH, l'ionisation par impact, la résistance distribuée de l'émetteur, l'auto-échauffement ainsi que l’effet tunnel induit par piégeage des électrons), ont été étalonnés dans la technologie BiCMOS055. L'étude de l’impact du budget thermique sur les performances des TBH SiGe dans des noeuds CMOS avancés (jusqu’au 14 nm) montre que le fT maximum peut atteindre 370 GHz dans une prochaine génération où les profils verticaux du BiCMOS055 seraient ‘simplement’ adaptés à l’optimisation du budget thermique total. Enfin, l'architecture TBH SiGe EXBIC, prenant son nom d’une base extrinsèque épitaxiale isolée du collecteur, est choisie comme la candidate la plus prometteuse pour la prochaine génération de TBH dans une technologie BiCMOS FD-SOI dans un noeud 28 nm. L'optimisation en TCAD de cette architecture résulte en des performances électriques remarquables telles que 470 GHz fT et 870 GHz fMAX dans ce noeud technologique. / The ultimate objective of this thesis is to propose and evaluate a novel SiGe HBT architec-ture overcoming the limitation of the conventional Double-Polysilicon Self-Aligned (DPSA) archi-tecture using Selective Epitaxial Growth (SEG). This architecture is designed to be compatible with the 28-nm Fully Depleted (FD) Silicon On Insulator (SOI) CMOS with a purpose to reach the objec-tive of 400 GHz fT and 600 GHz fMAX performance in this node. In order to achieve this ambitious objective, several studies, including the exploration and comparison of different SiGe HBT architec-tures, 55-nm Si/SiGe BiCMOS TCAD calibration, Si/SiGe BiCMOS thermal budget study, investi-gating a novel architecture and its optimization, have been carried out. Both, the fabrication process and physical device models (incl. band gap narrowing, saturation velocity, high-field mobility, SRH recombination, impact ionization, distributed emitter resistance, self-heating and trap-assisted tunnel-ing, as well as band-to-band tunneling), have been calibrated in the 55-nm Si/SiGe BiCMOS tech-nology. Furthermore, investigations done on process thermal budget reduction show that a 370 GHz fT SiGe HBT can be achieved in 55nm assuming the modification of few process steps and the tuning of the bipolar vertical profile. Finally, the Fully Self-Aligned (FSA) SiGe HBT architecture using Selective Epitaxial Growth (SEG) and featuring an Epitaxial eXtrinsic Base Isolated from the Collector (EXBIC) is chosen as the most promising candidate for the 28-nm FD-SOI BiCMOS genera-tion. The optimization of this architecture results in interesting electrical performances such as 470 GHz fT and 870 GHz fMAX in this technology node.

Process variability is a major challenge for the design of nano scale MOSFETs due to fundamental physical limits as well as process control limitations. As the size of the devices is scales down to improve performance, the circuit becomes more sensitive to the process variations. Thus, it is necessary to have a device model that can predict the variations of device characteristics. Statistical modeling method is a potential solution for this problem. The novelty of the work is that we connect BSIM parameters directly to the underlying process parameters. This is very useful for fabs to optimize and control the specific processes to achieve certain circuit metric. This methodology and framework is extendable to any future technologies, because we used a device independent, but process depended frame work In the first part of this thesis, presents the design of nominal MOS devices with 28 nm physical gate length. The device is optimized to meet the specification of low standby power technology specification of International Technology Roadmap for Semiconductors ITRS(2012). Design of experiments are conducted and the following parameters gate length, oxide thickness, halo concentration, anneal temperature and title angle of halo doping are identified as the critical process parameters. The device performance factors saturation current, sub threshold current, output impendence and transconductance are examined under process variabilty. In the subsequent sections of the thesis, BSIM parameter extraction of MOS devices using the software ICCAP is presented. The variability of the spice parameters due to process variation is extracted. Using the extracted data a new BSIM interpolated model for a variability aware circuit design is proposed assume a single process parameter is varying. The model validation is done and error in ICCAP extraction method for process variability is less than 10% for all process variation condition in 3σ range. In the next section, proposes LUT model and interpolated method for a variability aware circuit design for single parameter variation. The error in LUT method for process variability reports less than 3% for all process variation condition in 3σ range. The error in perdition of drain current and intrinsic gain for LUT model files are very close to the result of device simulation. The focus of the work was to established effective method to interlink process and SPICE parameters under variability. This required generating a large number of BSIM parameter ducks. Since there could be some inaccuracy in large set of BSIM parameters, we used LUT as a golden standard. We used LUT modeling as a benchmark for validation of our BSIM3 model In the final section of thesis, impact of multi parameter variation of the processes in device performance is modelled using RSM method; the model is verified using ANOVA method. Models are found to be sufficient and stable. The reported error is less than 1% in all cases. Monte Carlo simulation confirms stability and repeatability of the model. The model for random variabilty of process parameters are formulated using BSIM and compared with the LUT model. The model was tested using a benchmark circuit. The maximum error in Monte Carlo simulation is found to be less than 3% for output current and less than 8% for output impedance.

Die vorliegende Arbeit beschäftigt sich mit dem Aufbau und der Durchführung eines Teststand für Gateoxidstresstests mit einer gestuften Anhebung der Spannung und einer anschließenden Datenauswertung, um den Anwendern eine Möglichkeit zur Ermittlung der extrinsischen und intrinsischen Fehler von Bauelementen zu ermöglichen. Hierbei wurden Unterschiede zwischen den verschiedenen Herstellern von Si-IGBTs und SiC-MOSFETs gefunden und auch zwischen verschiedenen Bauelementtypen des gleichen Herstellers von SiC-MOSFETs. Zusätzlich dazu wurden die geltenden Empfehlungen für Heißsperrdauertests und Sperrtests unter feuchter Wärme auf die Nutzbarkeit für Anwender untersucht. Hierbei zeigt sich, dass in Hinblick auf die höhere Betriebstemperatur der Bauelemente die geltenden Empfehlungen für Heißsperrdauertests überarbeitet werden sollte. Für die anwendungsnahe Durchführung eines Sperrtests unter feuchter Wärme sollten ebenfalls die geltenden Empfehlungen überarbeitet werden, da für Bauelemente mit größeren Sperrspannungen als 100 V, die Sperrspannung in der Anwendung über 80 V liegt.:Inhaltsverzeichnis Abkürzungsverzeichnis Formelverzeichnis Vorwort 1 Einleitung 2 Dielektrika in Leistungsbauelementen 2.1 Anwendungen und Anforderungen an Dielektrika in Leistungshalbleitern 2.1.1 Passivierung 2.1.2 Gateoxid 2.2 Alterungsmechanismen von Dielektrika 2.2.1 Ladungen, Haftstellen bzw. Fehler im Oxid 2.2.2 Das E-Modell 2.2.3 Das 1/E-Modell 2.2.4 Zusammenspiel der beiden Mechanismen 2.2.5 Elektrochemische Migration 2.3 Grenzfläche von Dielektrika und Halbleiter 2.4 Beschleunigungsmodelle 2.4.1 Das Arrhenius-Modell 2.4.2 Das Exponential-Modell 2.4.3 Das Inverse Potenz Gesetz - IPL (Inverse Power Law) 2.4.4 Das Verallgemeinerte Eyring-Modell 2.4.5 Berechnung der Lebensdauer bei gestuften Beschleunigungstests am Beispiel eines gestuften Gatestresstests mit Anwendung des verallgemeinerten Eyring-Modells 3 Experimenteller Aufbau 3.1 HTRB - High Temperature Reverse Bias Test 3.2 H3TRB - High Humidity High Temperature Reverse Bias Test 3.2.1 Testaufbau des H3TRB 3.2.2 Teststrategie des H3TRB 3.3 HTGS -Hochtemperatur Gatestresstest 3.3.1 Testaufbau des HTGS 3.3.2 Teststrategie des HTGS 3.4 Testauswertung 4 Experimentelle Ergebnisse 4.1 Ergebnisse des HTRB 4.1.1 Diskrete Bauelemente - D2Pak und CanPAK 4.1.2 HTRB SiC-Bauelemente 4.2 Ergebnisse des H3TRB 4.2.1 Test von Silicon-Vergussmassen 4.2.2 Diskrete Bauelemente - D2Pak und CanPAK 4.2.3 SiC-MOSFET-Modul 4.2.4 SiC-Dioden 4.3 Ergebnisse des HTGS 4.3.1 HTGS - IGBTs 4.3.2 HTGS - SiC-MOSFET 5 Zusammenfassung und Ausblick Anhang A Daten H3TRB Projekt HiT-Modul B Verwendete Geräte B.1 Sperrmessung B.2 Thresholdspannungsmessung B.3 Mikroskop B.4 Klimakammer Literaturverzeichnis Abbildungsverzeichnis Tabellenverzeichnis Lebenslauf

La presente Tesis Doctoral sigue el formato por compendio de publicaciones, en la que se han incluido cuatro artículos, tres de ellos publicados en revistas de alto factor de impacto Journal Citations Report; JCR Q1, y un artículo en proceso de revisión en una revista también de alto factor de impacto JCR Q1. La transmisión del Virus de la Inmunodeficiencia Humana (VIH) sigue siendo un problema de salud pública. En los últimos años se ha visto incrementado el porcentaje de nuevos casos de personas infectadas por este virus, llegando a desarrollar el Síndrome de Inmunodeficencia adquirida (SIDA), lo que conlleva una disminución de la Calidad de Vida Relacionada con la Salud (CVRS) de aquellas personas que lo padecen. Dicho aumento en la transmisión de este virus se ha visto incrementado en mayor medida entre la población joven, por lo que es de gran relevancia indagar e identificar aquellos factores de riesgo que propician la adquisición del VIH en este colectivo. Es por todo ello, que la presente tesis doctoral se dirige al estudio de los factores de riesgo y protección relacionados con variables biopsicosociales y del estilo de vida para el contagio del VIH, así como en la evaluación y asociación del estilo de vida con la Calidad de Vida Relacionada con la Salud en población que convive con la infección por VIH. Para ello, en el primer estudio se contó con una muestra de 335 estudiantes universitarios españoles y se evaluaron factores sociodemográficos, estilos de vida y variables de riesgo de transmisión del VIH. Se establecieron diferencias respecto a las características sociodemográficas (edad, sexo, estado civil, situación laboral, situación económica y orientación sexual) y estilo de vida (dieta, ejercicio físico, tabaquismo, consumo de alcohol y estrés). Los resultados obtenidos indicaron que, en general, ser mayor, estar en pareja y estar empleado son factores relacionados con un alto riesgo de transmisión del VIH. En cuanto al estilo de vida, la mala alimentación, una menor intensidad en la práctica de ejercicio físico, la mayor ingesta de alcohol y el tabaquismo se asociaron significativamente con un mayor riesgo de transmisión del VIH, a través de un menor uso del preservativo y una mayor frecuencia de conductas sexuales de riesgo. En este sentido, los participantes que desarrollan un estilo de vida poco saludable tienen el doble de probabilidad de tener un alto riesgo de transmisión del VIH, especialmente con respecto a estos comportamientos previamente indicados. Con el objetivo de analizar en mayor profundidad la relación entre los estilos de vida y el riesgo de transmisión de VIH, en el segundo estudio se analizó la relación entre la adherencia al Estilo de Vida Mediterráneo (EVM), caracterizado por establecer una adherencia a la dieta mediterránea, un alto nivel de socialización y comunicación durante el cocinado o consumo de los alimentos, realización de actividad física regular y buena calidad del sueño, con el funcionamiento y conductas de riesgo para la salud asociadas a la transmisión del VIH. Para ello, se evaluó la asociación entre la adherencia al EVM con el funcionamiento cognitivo, principalmente síntomas prefrontales, y conductas de riesgo para la transmisión del VIH. La muestra estuvo compuesta por 328 estudiantes universitarios españoles con un rango de edad entre 18 y 30 años. Los resultados obtenidos mostraron una asociación significativa entre el EVM, los síntomas prefrontales y conductas de riesgo para el contagio de VIH. Los participantes con una alta adherencia al EVM mostraron un menor riesgo de contagio de VIH, ya que presentaron más información sobre el virus, conductas sexuales más seguras y una mayor frecuencia de uso de del preservativo. Los síntomas prefrontales en el dominio ejecutivo mediaron la relación entre EVM y las actitudes y la autoeficacia hacia el uso del preservativo. De esta manera, una mayor adherencia al EVM se relacionó con un menor número de síntomas prefrontales, y, por tanto, con una mayor autoeficacia y actitud positiva hacia el uso del preservativo. Una vez analizada la influencia de los estilos de vida sobre el riesgo de transmisión del VIH en población general, se hacía necesario analizar los estilos de vida en población con VIH, y de la misma manera, analizar la relación de estas variables con el riesgo de transmisión del virus y con el estado de salud. Dada que la transmisión del VIH ha aumentado y con ella, el número de personas infectadas, es importante evaluar aquellos factores del estilo de vida, fundamentalmente relacionados con las prácticas sexuales, y su relación con la CVRS en este grupo de población. Tras la realización de una exhaustiva revisión bibliográfica, se encontró que el cuestionario Medical Outcome Study - HIV Health Survey (MOS-HIV) es uno de los instrumentos más utilizados para la evaluación de la CVRS en personas que viven con el VIH, tanto en contextos clínicos como en estudios de investigación. Por ello, en el tercer estudio de esta tesis doctoral, se estimó la fiabilidad promedio de las puntuaciones del cuestionario MOS-HIV y se evaluaron las características de los estudios que podrían explicar la variabilidad entre las estimaciones de fiabilidad. Además, se estimó la tasa de inducción de la fiabilidad del MOS-HIV. Para ello, se realizó una revisión sistemática de la literatura previa, que incluyó estudios que informaron de coeficientes α y/o test-retest con los datos disponibles para la puntuación total del MOS-HIV y sus diferentes subescalas. Se incluyeron 50 estudios (N= 14.132) en el metanálisis de generalización de la fiabilidad. El coeficiente α promedio para la puntuación total de MOS-HIV fue de .91 y superior a .80 para todas las subescalas, excepto para el RF (funcionamiento de rol), que obtuvo un coeficiente de fiabilidad promedio de .76. Además, se encontró que la inducción de fiabilidad en los diferentes estudios analizados era del 76,1%. Los resultados obtenidos en el presente estudio indicaron que el MOS-HIV es un instrumento fiable para la evaluación de la CVRS en personas que conviven con el VIH, con fines clínicos y de investigación. Una vez que se identificó que el cuestionario MOS-HIV es un instrumento válido y fiables para la evaluación de la CVRS en población con VIH, el cuarto estudio se dirigió a analizar los efectos de los estilos de vida, fundamentalmente relacionados con las prácticas sexuales, sobre la CVRS en población con VIH. En este sentido, en los últimos años no solamente ha aumentado la transmisión de VIH, sino que también han aparecido nuevas prácticas sexuales que favorecen dicha transmisión. Una de estas nuevas prácticas es el Chemsex, es decir, un nuevo comportamiento sexual de riesgo que implica la participación en relaciones sexuales bajo la influencia del efecto de diferentes drogas. Estas nuevas prácticas sexuales de riesgo han mostrado un aumento significativo durante los últimos años, lo que conlleva un grave problema de salud pública, especialmente cuando el Chemsex es practicado por personas con un diagnóstico de VIH. Por ello, se analizaron las características de las prácticas de Chemsex, las prácticas sexuales asociadas y los resultados de salud en una muestra de 101 hombres con VIH que tienen sexo con hombres que acudían al Servicio de Enfermedades Infecciosas del Hospital General Universitario de Alicante (España). Además, también se analizó la asociación entre la práctica de Chemsex y la CVRS. El Chemsex y las prácticas sexuales se evaluaron empleando un cuestionario aplicado ad hoc. La CVRS se evaluó mediante el cuestionario MOS-HIV. En total, el 40,6% de los participantes había practicado Chemsex durante el último año. Cuando se compararon las prácticas sexuales entre los individuos que practicaban Chemsex y los que no, los primeros presentaron un mayor nivel de conductas sexuales de riesgo, especialmente con parejas sexuales ocasionales y múltiples. En cuanto a la CVRS, aquellos individuos que practicaron Chemsex presentaron una peor CVRS en la mayoría de los dominios, especialmente aquellos participantes que lo practicaban con mayor intensidad. La presente Tesis Doctoral aporta información relevante acerca del VIH, su transmisión y su afectación sobre la CVRS en las personas que lo presentan. Se destaca la relevancia de las características sociodemográficas y los estilos de vida en la propensión a desarrollar conductas de riesgo para la infección por VIH, así como la importancia del estilo de vida mediterráneo en la prevención de estas conductas de riesgo, especialmente a través de un adecuado funcionamiento cognitivo. Además, se ha identificado al cuestionario MOS-HIV como “gold estándar” para la evaluación de la CVRS en personas con VIH. Finalmente, se destaca la alta prevalencia de la práctica de Chemsex entre hombres con VIH que tienen sexo con hombres en España y se especifican los efectos negativos que tienen estas prácticas sobre la CVRS, probablemente debido a los efectos mixtos de niveles más altos de conductas sexuales de riesgo y las consecuencias del consumo de drogas.

Ferroelectric field effect transistor (FeFET) memories based on a new type of ferroelectric material (silicon doped hafnium oxide) were studied within the scope of the present work. Utilisation of silicon doped hafnium oxide (Si:HfO2) thin films instead of conventional perovskite ferroelectrics as a functional layer in FeFETs provides compatibility to the CMOS process as well as improved device scalability. The influence of different process parameters on the properties of Si:HfO2 thin films was analysed in order to gain better insight into the occurrence of ferroelectricity in this system. A subsequent examination of the potential of this material as well as its possible limitations with the respect to the application in non-volatile memories followed. The Si:HfO2-based ferroelectric transistors that were fully integrated into the state-of-the-art high-k metal gate CMOS technology were studied in this work for the first time. The memory performance of these devices scaled down to 28 nm gate length was investigated. Special attention was paid to the charge trapping phenomenon shown to significantly affect the device behaviour.:1 Introduction 2 Fundamentals 2.1 Non-volatile semiconductor memories 2.2 Emerging memory concepts 2.3 Ferroelectric memories 3 Characterisation methods 3.1 Memory characterisation tests 3.2 Ferroelectric memory specific characterisation tests 3.3 Trapping characterisation methods 3.4 Microstructural analyses 4 Sample description 4.1 Metal-insulator-metal capacitors 4.2 Ferroelectric field effect transistors 5 Stabilisation of the ferroelectric properties in Si:HfO2 thin films 5.1 Impact of the silicon doping 5.2 Impact of the post-metallisation anneal 5.3 Impact of the film thickness 5.4 Summary 6 Electrical properties of the ferroelectric Si:HfO2 thin films 6.1 Field cycling effect 6.2 Switching kinetics 6.3 Fatigue behaviour 6.4 Summary 7 Ferroelectric field effect transistors based on Si:HfO2 films 7.1 Effect of the silicon doping 7.2 Program and erase operation 7.3 Retention behaviour 7.4 Endurance properties 7.5 Impact of scaling on the device performance 7.6 Summary 8 Trapping effects in Si:HfO2-based FeFETs 8.1 Trapping kinetics of the bulk Si:HfO2 traps 8.2 Detrapping kinetics of the bulk Si:HfO2 traps 8.3 Impact of trapping on the FeFET performance 8.4 Modified approach for erase operation 8.5 Summary 9 Summary and Outlook

科学研究費補助金 研究種目:基盤研究(A)(2) 課題番号:13305005 研究代表者:近藤 博基 研究期間:2001-2004年度

Este projeto nasceu inserido num contexto de crescentes pesquisas em direção à construção de um cabedal de conhecimento acerca das ciências ambientais que tratam e estudam a dinâmica dos reservatórios de carbono e suas contribuições para o Efeito Estufa. Extrapolações de novos mapas digitalizados de solos sugerem que os espodossolos hidromórficos da Amazônia podem estar com uma contagem de carbono subestimada em até 12,3 Pg de C e trabalhos anteriores mostram que o carbono imobilizado neste perfil pode sofrer mineralização devido ao corte na rede de drenagem ou rebaixamento do nível freático, podendo assim contribuir em grande parte para o aumento de emissão dos Gases do Efeito Estufa. Nesta circunstância, coube a este trabalho, caracterizar espectroscopicamente, a matéria orgânica estocada em profundidade em 9 perfis de solo da região de São Gabriel da Cachoeira - AM, na floresta amazônica. Foram analisadas 127 amostras em quantidade de carbono e por fluorescência induzida por laser (FIL). A partir destas análises preliminares, foi possível selecionar 12 amostras de 2 perfis para análise mais detalhada através da extração das substâncias húmicas. Foram realizadas análises para obtenção da textura destes perfis, análise dos ácidos húmicos como relação C/N, espectroscopia de infravermelho com transformada de Fourier (FTIR), RMN de 13C no estado sólido, fluorescências bidimensional e tridimensional com aplicação do método estatístico análise dos fatores paralelos (PARAFAC) e também análise dos ácidos fúlvicos como carbono orgânico total (TOC), espectroscopia na região do ultra-violeta e visível e fluorescência 3D associada ao PARAFAC. Em geral, as amostras se dividiram em 3 grupos diferentes, onde a matéria orgânica em superfície se mostrou lábil e recente, a matéria orgânica nos horizontes B húmicos se mostraram com características recalcitrantes e a matéria orgânica contida nos horizontes onde existia água livre (lençol freático), se mostraram com características diferentes, indicando não serem tão jovens quanto as em superfície, porém mais jovens do que a armazenada no Bh, devido a uma possível migração por movimentos laterais do lençol freático. A correlação entre os resultados mostrou que a textura do solo é importante para o acúmulo da matéria orgânica e conseqüentemente sua humificação. Os resultados de fluorescência corroboraram a interpretação dos dados de RMN, FTIR e textura, apontando que o Perfil 4 (mais próximo ao rio) por ter C2 maior nos horizontes intermediários, contém maior quantidade de exsudatos microbianos frescos. Para o Perfil 5, que é uma mancha de Espodossolo dentro de um Latossolo e encontra-se mais longe do rio, os fluoróforos mais representativos são oriundos de anéis aromáticos mais antigos e conseqüentemente mais humificados, devido às maiores intensidades de C1 e C3. Vale ressaltar que esta interpretação se alinha com os resultados de datação do 14C desta região. Foi notório que a humificação ocorre a partir do começo do horizonte Bh e que seu acúmulo pode ocorrer tanto nos horizontes intermediários (Bh) quanto mais os profundos (úmidos). Dessa forma, pode-se concluir que uma drenagem excessiva das bordas dos rios nesta região que acumula carbono em profundidade, poderá expor a MO guardada e estocada a longo tempo, contribuindo para o aumento da temperatura global e por conseguinte catalisando um desequilíbrio no clima da sua maior reguladora no mundo: a Floresta Amazônica. / This project was born inserted in a context of increasing research towards building knowledge about environmental science that treat and study the dynamics of carbon reservoirs and their contribution to the greenhouse. Extrapolation of new digital soil maps suggests that Amazonian hydromorphic Spodosols may be with a carbon accounting underestimated by up to 12.3 Pg of C and previous work show that the carbon fixed in this profile may suffer mineralization due to the cut in the drainage network or lowering of the water level and can contribute largely to the increased emission of greenhouse gas. In this circumstance, it was instructed to this work, the spectroscopic characterization, of the stored organic matter in depth at 9 soil profiles of São Gabriel da Cachoeira - AM, in the Amazon rainforest. 127 samples were analyzed for amount of carbon and laser-induced fluorescence (LIF). From these preliminary analyzes, it was possible to select 12 samples of 2 profiles for humic substances extraction and further detailed analysis. Analyzes were conducted to obtain the texture of these profiles, analysis of humic acids as C/N ratio, Fourier Transform Infrared Spectroscopy (FTIR), solid state 13C NMR, two and three dimensional fluorescence with applying of the Parallel factors analysis (PARAFAC) statistical method and also fulvic acid analysis as Total Organic Carbon (TOC), ultra-violet and visible region spectroscopy and 3D fluorescence associated with PARAFAC. In general, the samples were divided into 3 different groups, wherein the surface organic matter evinced labile and recent. The B humic horizons organic matter proved recalcitrant characteristics and organic matter contained in horizons which had free water (groundwater), showed different characteristic, indicating they are not so young as the surface, but younger than stored in Bh, because of possible migration by lateral movements of the water table. The correlation between the results showed that soil texture is important for the accumulation of organic matter and therefore its humification. The fluorescence results confirmed the interpretation of the NMR, FTIR and texture datas, indicating that the profile 4 (closest to the river), presenting major C2 in intermediate horizons, contains larger amount of fresh microbial exudates. To profile 5, which is a Spodosol spot within a Ferrasol and is thither from the river, the most representative fluorophores came from older aromatic rings and therefore is more humified, due to higher intensities C1 and C3. It is noteworthy that this interpretation is in accord with the results of 14C dating of samples from this region. It was clear that the humification occurs from the beginning of the Bh horizon and their accumulation can occur both in the intermediate horizons (Bh) and in deeper (wet). Thus, it can be concluded that excessive drainage of the edges of rivers in this region that collects carbon in depth, may expose the OM stored for long time, contributing to increase the overall temperature and therefore catalyzing an imbalance in the climate of the biggest regulatory of it in the world: the Amazon rainforest.

Este projeto nasceu inserido num contexto de crescentes pesquisas em direção à construção de um cabedal de conhecimento acerca das ciências ambientais que tratam e estudam a dinâmica dos reservatórios de carbono e suas contribuições para o Efeito Estufa. Extrapolações de novos mapas digitalizados de solos sugerem que os espodossolos hidromórficos da Amazônia podem estar com uma contagem de carbono subestimada em até 12,3 Pg de C e trabalhos anteriores mostram que o carbono imobilizado neste perfil pode sofrer mineralização devido ao corte na rede de drenagem ou rebaixamento do nível freático, podendo assim contribuir em grande parte para o aumento de emissão dos Gases do Efeito Estufa. Nesta circunstância, coube a este trabalho, caracterizar espectroscopicamente, a matéria orgânica estocada em profundidade em 9 perfis de solo da região de São Gabriel da Cachoeira - AM, na floresta amazônica. Foram analisadas 127 amostras em quantidade de carbono e por fluorescência induzida por laser (FIL). A partir destas análises preliminares, foi possível selecionar 12 amostras de 2 perfis para análise mais detalhada através da extração das substâncias húmicas. Foram realizadas análises para obtenção da textura destes perfis, análise dos ácidos húmicos como relação C/N, espectroscopia de infravermelho com transformada de Fourier (FTIR), RMN de 13C no estado sólido, fluorescências bidimensional e tridimensional com aplicação do método estatístico análise dos fatores paralelos (PARAFAC) e também análise dos ácidos fúlvicos como carbono orgânico total (TOC), espectroscopia na região do ultra-violeta e visível e fluorescência 3D associada ao PARAFAC. Em geral, as amostras se dividiram em 3 grupos diferentes, onde a matéria orgânica em superfície se mostrou lábil e recente, a matéria orgânica nos horizontes B húmicos se mostraram com características recalcitrantes e a matéria orgânica contida nos horizontes onde existia água livre (lençol freático), se mostraram com características diferentes, indicando não serem tão jovens quanto as em superfície, porém mais jovens do que a armazenada no Bh, devido a uma possível migração por movimentos laterais do lençol freático. A correlação entre os resultados mostrou que a textura do solo é importante para o acúmulo da matéria orgânica e conseqüentemente sua humificação. Os resultados de fluorescência corroboraram a interpretação dos dados de RMN, FTIR e textura, apontando que o Perfil 4 (mais próximo ao rio) por ter C2 maior nos horizontes intermediários, contém maior quantidade de exsudatos microbianos frescos. Para o Perfil 5, que é uma mancha de Espodossolo dentro de um Latossolo e encontra-se mais longe do rio, os fluoróforos mais representativos são oriundos de anéis aromáticos mais antigos e conseqüentemente mais humificados, devido às maiores intensidades de C1 e C3. Vale ressaltar que esta interpretação se alinha com os resultados de datação do 14C desta região. Foi notório que a humificação ocorre a partir do começo do horizonte Bh e que seu acúmulo pode ocorrer tanto nos horizontes intermediários (Bh) quanto mais os profundos (úmidos). Dessa forma, pode-se concluir que uma drenagem excessiva das bordas dos rios nesta região que acumula carbono em profundidade, poderá expor a MO guardada e estocada a longo tempo, contribuindo para o aumento da temperatura global e por conseguinte catalisando um desequilíbrio no clima da sua maior reguladora no mundo: a Floresta Amazônica. / This project was born inserted in a context of increasing research towards building knowledge about environmental science that treat and study the dynamics of carbon reservoirs and their contribution to the greenhouse. Extrapolation of new digital soil maps suggests that Amazonian hydromorphic Spodosols may be with a carbon accounting underestimated by up to 12.3 Pg of C and previous work show that the carbon fixed in this profile may suffer mineralization due to the cut in the drainage network or lowering of the water level and can contribute largely to the increased emission of greenhouse gas. In this circumstance, it was instructed to this work, the spectroscopic characterization, of the stored organic matter in depth at 9 soil profiles of São Gabriel da Cachoeira - AM, in the Amazon rainforest. 127 samples were analyzed for amount of carbon and laser-induced fluorescence (LIF). From these preliminary analyzes, it was possible to select 12 samples of 2 profiles for humic substances extraction and further detailed analysis. Analyzes were conducted to obtain the texture of these profiles, analysis of humic acids as C/N ratio, Fourier Transform Infrared Spectroscopy (FTIR), solid state 13C NMR, two and three dimensional fluorescence with applying of the Parallel factors analysis (PARAFAC) statistical method and also fulvic acid analysis as Total Organic Carbon (TOC), ultra-violet and visible region spectroscopy and 3D fluorescence associated with PARAFAC. In general, the samples were divided into 3 different groups, wherein the surface organic matter evinced labile and recent. The B humic horizons organic matter proved recalcitrant characteristics and organic matter contained in horizons which had free water (groundwater), showed different characteristic, indicating they are not so young as the surface, but younger than stored in Bh, because of possible migration by lateral movements of the water table. The correlation between the results showed that soil texture is important for the accumulation of organic matter and therefore its humification. The fluorescence results confirmed the interpretation of the NMR, FTIR and texture datas, indicating that the profile 4 (closest to the river), presenting major C2 in intermediate horizons, contains larger amount of fresh microbial exudates. To profile 5, which is a Spodosol spot within a Ferrasol and is thither from the river, the most representative fluorophores came from older aromatic rings and therefore is more humified, due to higher intensities C1 and C3. It is noteworthy that this interpretation is in accord with the results of 14C dating of samples from this region. It was clear that the humification occurs from the beginning of the Bh horizon and their accumulation can occur both in the intermediate horizons (Bh) and in deeper (wet). Thus, it can be concluded that excessive drainage of the edges of rivers in this region that collects carbon in depth, may expose the OM stored for long time, contributing to increase the overall temperature and therefore catalyzing an imbalance in the climate of the biggest regulatory of it in the world: the Amazon rainforest.